KR101791051B1 - Method of the convrsion of polycyclic aromatic hydrocarbons into btx-rich monocyclic aromatic hydrocarbons - Google Patents
Method of the convrsion of polycyclic aromatic hydrocarbons into btx-rich monocyclic aromatic hydrocarbons Download PDFInfo
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- KR101791051B1 KR101791051B1 KR1020150033643A KR20150033643A KR101791051B1 KR 101791051 B1 KR101791051 B1 KR 101791051B1 KR 1020150033643 A KR1020150033643 A KR 1020150033643A KR 20150033643 A KR20150033643 A KR 20150033643A KR 101791051 B1 KR101791051 B1 KR 101791051B1
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- C07C4/26—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting polyaryl compounds at a bond between uncondensed six-membered aromatic rings, e.g. biphenyl to benzene
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Abstract
The present invention relates to a method for purifying a single ring aromatic hydrocarbon through partial hydrogenation and hydrocracking processes in the presence of a hydrocracking catalyst from oil containing a large amount of polycyclic aromatic compounds including PFO (pyrolysis fuel oil) and LCO (light cycle oil) . According to the present invention, it is possible to provide a method for producing an aromatic product, which can produce an aromatic compound of high added value as a product by using PFO and LCO as raw materials. In addition, according to the present invention, it is possible to provide a method for producing an aromatic product with a high yield by varying the conditions of the hydrodesulfurization / denitrification process and the hydrocracking reaction process depending on the characteristics (S, N, aromatic content) of the polycyclic aromatic oil. In addition, the present invention can provide a method for producing aromatic products having a high added value of low sulfur, low nitrogen and low-pollution, which are excellent in the hydrogen desulfurization / denitrification and decomposition reaction effects.
Description
The present invention relates to a method for converting from an oil having a large amount of a polycyclic aromatic compound including PFO (pyrolysis fuel oil) and LCO (light cycle oil) to a single ring aromatic hydrocarbon through partial hydrogenation and hydrocracking in the presence of a hydrocracking catalyst .
Light cycle oil (LCO) and pyrolysis fuel oil (PFO), which are mixed in the fluidized bed catalytic cracking (FCC) process, and pyrolysis fuel oil (PFO) Compounds, they are mostly sold as low-cost heavy fuel oil or exhausted as self-fuel.
In recent years, a technology has been proposed for converting polycyclic aromatic oil such as PFO and LCO into BTX (benzene-toluene-xylene), mainly in the United States (UOP) and Japan (Toray, JX Nippon Oil, These high-value-added technologies are based on catalyst and process technology, and the following methods are reported:
[1] A method of converting LCO into BTX by hydrotreating and hydrocracking (Patent Document 1)
[2] A method in which PFO is distilled to separate a tricyclic aromatic and converted to BTX through partial hydrogenation and catalytic decomposition of a bicyclic aromatic (Patent Document 2)
[3] A method of recovering BTX after purification by catalytic cracking of LCO and hydrogenation (Patent Document 3)
[4] A method for producing BTX by decomposing LCO under a zeolite catalyst for catalytic cracking (Patent Document 4)
[5, 6] A method including catalytic cracking of LCO followed by 3-ring aromatic separation, hydrogenation, BTX separation purification, and recycling of heavy components and hydrogen (Patent Literature 5 and Patent Literature 6).
The BTX yields given in the above methods for converting low-cost heavy oil fractions containing polycyclic aromatic compounds are not high enough. That is, in Patent Document 1, there are no examples other than the process concept, and thus the effectiveness has not been proved. Further improvement is required in the BTX yields shown in Patent Documents 2 to 6 within 50%. In Patent Documents 2 to 6, since the simulated LCO is applied, there is a problem that it is difficult to confirm the influence on the substantial amount of sulfur and nitrogen compounds remaining in the actual LCO.
DISCLOSURE Technical Problem The present invention has been made to solve the above-mentioned problems of the prior art and the technical problems required from the past, and it is an object of the present invention to provide a method of hydrodesulfurization / denitrification And a process for producing aromatic products with high yield by varying the conditions of the hydrocracking reaction process.
The present invention also provides a process for producing an aromatic product using PFO and LCO as raw materials and using a shape-selective catalyst.
In order to solve the above problems, the present invention provides a method for obtaining a monocyclic aromatic compound by hydrodesulfurization, denitrification, partial hydrogenation and hydrocracking from an oil containing an aromatic compound generated in the refining process of crude oil do.
The oil may be selected from the group consisting of PFO (pyrolysis fuel oil), LCO (light cycle oil), pyrolysis gasoline, heavy aromatic compounds, atmospheric gas oil, fluid catalytic cracking gasoline, light cracking naphtha, heavy cracking naphtha, Which is composed of light oil, coker gas oil, coker diesel, coker naphtha, heavy and reduced petroleum crude oil, oil under atmospheric distillation suspension, oil under reduced pressure distillation, pitch, asphalt, bitumen, tar sands oil, It is preferable to select at least one member from the group.
The hydrodesulfurization, denitrification and partial hydrogenation processes and the hydrocracking reaction process are preferably operated in a batch reactor, a continuous fixed bed reactor or a continuous fluidized bed reactor.
The monocyclic aromatic compound is preferably selected from the group consisting of benzene, toluene and xylene.
In the first aspect of the present invention, it is preferable that the hydrodesulfurization, denitrification, partial hydrogenation and hydrocracking reaction processes are hydrotreated complex reaction processes operated simultaneously.
It is preferable that the oil to be fed to the hydrogenation complex reaction process is PFO.
The hydrotreating complex reaction process is preferably operated by injecting hydrogen and a shape selective catalyst.
The shape-selective catalyst is preferably a metal component selected from the group consisting of Group 6, Group 8, Group 9 and Group 10 of the periodic table.
The metal component is preferably selected from the group consisting of Ni 2 P, Co 2 P, Fe 2 P, MoP, WP, MoS 2 , Ni-MoS 2 , Ni-WS 2 and Co-MoS 2 .
The shape-selective catalyst preferably further comprises at least one shape-selective carrier selected from the group consisting of zeolite, ZSM-5, beta zeolite, Y-zeolite, USY-zeolite, mordenite and silica alumina.
The hydrotreated complex reaction process is operated under conditions of a temperature of 200 to 1,000 ° C., a hydrogen partial pressure of 10 to 200 atm, a hydrogen content of 50 to 400 Nm 3 / kL, and a LHSV (liquid hourly space velocity) of 0.5 to 10.0 hr -1 .
It is preferable to further include a distillation separation step prior to the hydrotreating complex reaction step.
With regard to the first aspect of the present invention, the method of obtaining the monocyclic aromatic compound of the present invention is characterized in that PFO (pyrolysis fuel oil) is fed into a distillation separation process and operated to produce a sulfur compound, a nitrogen compound, Separating an effluent comprising an aromatic compound and a residue comprising a triple or more aromatic compound and introducing the effluent into a hydrotreated complex reaction process wherein the hydrotreated complex reaction process is carried out in the presence of hydrogen and a shape selective catalyst , Hydrodesulfurization, denitrification and partial hydrogenation processes and hydrocracking reaction processes are simultaneously operated to remove unconverted oil fractions containing sulfur compounds, nitrogen compounds and bicyclic aromatic compounds to obtain a single ring aromatic compound .
The shape-selective catalyst is preferably Ni 2 P supported on beta zeolite.
In the second aspect of the present invention, it is preferable that the oil introduced into the hydrodesulfurization, denitrification and partial hydrogenation processes is LCO.
The hydrodesulfurization, denitrification, and partial hydrogenation processes are preferably operated by introducing hydrogen and a catalyst.
The catalyst is preferably a metal component selected from the group consisting of Group 6, Group 8, Group 9 and Group 10 of the periodic table.
The metal component is preferably selected from the group consisting of Ni 2 P, Co 2 P, Fe 2 P, MoP, WP, MoS 2 , Ni-MoS 2 , Ni-WS 2 and Co-MoS 2 .
The catalyst preferably further comprises at least one carrier selected from the group consisting of silica, alumina and silica alumina.
The hydrogen desulfurization, denitrification and partial hydrogenation processes are carried out at a temperature of 200 to 500 ° C., a hydrogen partial pressure of 10 to 100 atm, a hydrogen content of 50 to 400 Nm 3 / kL, a liquid hourly space velocity (LHSV) of 0.5 to 5.0 hr -1 It is preferable to operate under the conditions.
The hydrocracking reaction process is preferably operated by introducing hydrogen and a shape-selective catalyst.
The shape-selective catalyst is preferably a metal component selected from the group consisting of Group 6, Group 8, Group 9 and Group 10 of the periodic table.
The metal component is preferably selected from the group consisting of Ni 2 P, Co 2 P, Fe 2 P, MoP, WP, MoS 2 , Ni-MoS 2 , Ni-WS 2 and Co-MoS 2 .
The shape-selective catalyst preferably further comprises at least one shape-selective carrier selected from the group consisting of zeolite, ZSM-5, beta zeolite, Y-zeolite, USY-zeolite, mordenite and silica alumina.
The hydrocracking reaction process is operated under the conditions of a temperature of 200 to 1,000 ° C., a hydrogen partial pressure of 10 to 200 atm, a hydrogen content of 50 to 400 Nm 3 / kl, and a LHSV (liquid hourly space velocity) of 0.5 to 10.0 hr -1 .
With regard to the second aspect of the present invention, the method of obtaining the monocyclic aromatic compound of the present invention is characterized in that LCO (light cycle oil) is added and operated in a hydrogen desulfurization and denitrification process in the presence of hydrogen and a catalyst, Removing the oil containing the compound and the nitrogen compound to obtain a partially hydrogenated oil fraction containing an aromatic compound and introducing and operating the partially hydrogenated oil fraction in the presence of hydrogen and a shape selective catalyst in a hydrocracking reaction process, And removing the unconverted oil containing the above aromatic compound to obtain a monocyclic aromatic compound.
It is preferable that the shape-selective catalyst is Ni 2 P supported on beta zeolite and having a Ni loading of 0.7 mmol / g.
According to the present invention, it is possible to provide a method for producing an aromatic product, which can produce an aromatic compound of high added value as a product by using PFO and LCO as raw materials. In addition, according to the present invention, it is possible to provide a method for producing an aromatic product with a high yield by varying the conditions of the hydrodesulfurization / denitrification process and the hydrocracking reaction process depending on the characteristics (S, N, aromatic content) of the polycyclic aromatic oil. In addition, the present invention can provide a method for producing aromatic products having a high added value of low sulfur, low nitrogen and low-pollution, which are excellent in the hydrogen desulfurization / denitrification and decomposition reaction effects.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a process diagram schematically illustrating a specific example of producing an aromatic product from a PFO associated with the first aspect of the present invention.
Fig. 2 is a schematic diagram showing a specific example of producing an aromatic product from the LCO associated with the second aspect of the present invention. Fig.
Hereinafter, the present invention will be described in detail.
The present invention relates to a process for the production of benzene, toluene, xylene and 1-ring aromatic hydrocarbons in high yields through hydrogenolysis, denitrification, partial hydrogenation and hydrocracking processes, for example from PFO and LCO, comprising a large amount of polycyclic aromatic compounds Provide a way to do it.
Accordingly, the present invention provides a method for obtaining a monocyclic aromatic compound from an oil containing an aromatic compound generated in a refinery process of crude oil through a hydrodesulfurization, a denitrification, a partial hydrogenation process and a hydrocracking reaction process.
The oil may be selected from the group consisting of PFO (pyrolysis fuel oil), LCO (light cycle oil), pyrolysis gasoline, heavy aromatic compounds, atmospheric gas oil, fluid catalytic cracking gasoline, light cracking naphtha, heavy cracking naphtha, Which is composed of light oil, coker gas oil, coker diesel, coker naphtha, heavy and reduced petroleum crude oil, oil under atmospheric distillation suspension, oil under reduced pressure distillation, pitch, asphalt, bitumen, tar sands oil, It is preferable to select at least one member from the group.
The hydrodesulfurization, denitrification and partial hydrogenation processes and the hydrocracking reaction process are preferably operated in a batch reactor, a continuous fixed bed reactor or a continuous fluidized bed reactor.
The monocyclic aromatic compound is preferably selected from the group consisting of benzene, toluene and xylene.
According to a first aspect of the present invention, there is provided a method of separating oil from an oil and an outflow passage through a distillation separation process, And removing at least one selected from a sulfur compound and a nitrogen compound from the effluent through a hydrogenation complex reaction process in which a hydrodesulfurization, a denitrification, a partial hydrogenation reaction process and a hydrocracking reaction process are simultaneously operated in the presence of a shape- To an aromatic product comprising at least one selected from benzene, toluene and xylene.
The distillation separation process is for separating the PFO used as a raw material according to the boiling range and the light oil is used for producing an aromatic product such as benzene, toluene and xylene, and the PFO is introduced into the distillation separation process, The oil containing the compound, the nitrogen compound and the aromatic compound having one or two benzene rings is separated from the outflow passage, and the oil containing the aromatic compound having three or more benzene rings is separated from the residual oil.
The hydrodesulfurization, denitrification, partial hydrogenation and hydrocracking processes of the present invention remove sulfur compounds and nitrogen compounds contained in the oil to produce low-pollution aromatic products having sulfur and nitrogen contents every week, Is carried out by reacting the effluent with hydrogen in the presence of the shape-selective catalyst for the hydrogenation reaction.
In a preferred embodiment of the present invention, the hydrodesulfurization, denitrification and partial hydrogenation processes and the hydrocracking reaction process are preferably a hydrogenated complex reaction process operated at the same time.
It is preferable that the oil to be fed to the hydrogenation complex reaction process is PFO.
The hydrotreating complex reaction process is preferably operated by injecting hydrogen and a shape selective catalyst.
The shape-selective catalyst is preferably a metal component selected from the group consisting of Group 6, Group 8, Group 9 and Group 10 of the periodic table.
The metal component is preferably selected from the group consisting of Ni 2 P, Co 2 P, Fe 2 P, MoP, WP, MoS 2 , Ni-MoS 2 , Ni-WS 2 and Co-MoS 2 .
The shape-selective catalyst preferably further comprises at least one shape-selective carrier selected from the group consisting of zeolite, ZSM-5, beta zeolite, Y-zeolite, USY-zeolite, mordenite and silica alumina.
The hydrotreated complex reaction process is operated under conditions of a temperature of 200 to 1,000 ° C., a hydrogen partial pressure of 10 to 200 atm, a hydrogen content of 50 to 400 Nm 3 / kL, and a LHSV (liquid hourly space velocity) of 0.5 to 10.0 hr -1 . The above-mentioned reaction condition is an optimum condition for allowing the hydrogenation and the decomposition reaction to coexist, and is a condition suitable for hydrotreating the feed oil by partial hydrogenation. If the reaction conditions are out of the above range, hydrogenation is disadvantageous in the high temperature range, and coke formation due to condensation may proceed between the reactants. If the reaction temperature is too low, the reaction does not proceed or the hydrogenation reaction proceeds and BTX conversion becomes difficult . Also, the effect of pressure is opposite to that of temperature. If the pressure is too high, hydrogenation predominates and paraffinic products may predominate. If the pressure is lower than the above range, coke formation by dehydrogenation Which is not preferable.
It is preferable to further include a distillation separation step prior to the hydrotreating complex reaction step. remind In the distillation separation process, the PFO oil used as a raw material is separated according to the boiling range, the light oil fraction is introduced into the hydrogenation complex reaction process, and the heavy oil fraction is used as the carbon material. Preferably, hydrocarbons having a boiling point of 300 DEG C or less are preferable.
With regard to the first aspect of the present invention, the method of obtaining the monocyclic aromatic compound of the present invention is characterized in that PFO (pyrolysis fuel oil) is fed into a distillation separation process and operated to produce a sulfur compound, a nitrogen compound, Separating an effluent comprising an aromatic compound and a residue comprising a triple or more aromatic compound and introducing the effluent into a hydrotreated complex reaction process wherein the hydrotreated complex reaction process is carried out in the presence of hydrogen and a shape selective catalyst , Hydrodesulfurization, denitrification and partial hydrogenation processes and hydrocracking reaction processes are simultaneously operated to remove unconverted oil fractions containing sulfur compounds, nitrogen compounds and bicyclic aromatic compounds to obtain a single ring aromatic compound .
The shape-selective catalyst is preferably Ni 2 P supported on beta zeolite.
A second aspect of the present invention is to provide a method for removing at least one selected from sulfur compounds and nitrogen compounds through hydrodesulfurization and denitrification processes, step; And converting the partially saturated component into an aromatic product comprising at least one selected from benzene, toluene and xylene through a hydrocracking reaction process in the presence of a shape selective catalyst. .
In the hydrodesulfurization and denitrification step, the LCO removes impurities such as sulfur compounds and nitrogen compounds contained in the oil in the presence of the catalyst, and the aromatic components including two or more aromatic rings are partially saturated.
The partially saturated feed obtained from the process is introduced into the hydrocracking process. In the hydrocracking reaction step, an aromatic compound having one or two benzene rings is subjected to hydrocracking reaction.
As a preferred embodiment, in the second aspect of the present invention, it is preferable that the oil to be fed to the hydrodesulfurization, denitrification and partial hydrogenation processes is LCO.
The hydrodesulfurization, denitrification, and partial hydrogenation processes are preferably operated by introducing hydrogen and a catalyst.
The catalyst is preferably a metal component selected from the group consisting of Group 6, Group 8, Group 9 and Group 10 of the periodic table.
The metal component is preferably selected from the group consisting of Ni 2 P, Co 2 P, Fe 2 P, MoP, WP, MoS 2 , Ni-MoS 2 , Ni-WS 2 and Co-MoS 2 .
The catalyst preferably further comprises at least one carrier selected from the group consisting of silica, alumina and silica alumina.
The hydrogen desulfurization, denitrification and partial hydrogenation processes are carried out at a temperature of 200 to 500 ° C., a hydrogen partial pressure of 10 to 100 atm, a hydrogen content of 50 to 400 Nm 3 / kL, a liquid hourly space velocity (LHSV) of 0.5 to 5.0 hr -1 It is preferable to operate under the conditions. The above-mentioned reaction condition is an optimum condition for allowing the hydrogenation and the decomposition reaction to coexist, and is a condition suitable for hydrotreating the feed oil by partial hydrogenation. If the reaction conditions are out of the above range, hydrogenation is disadvantageous in the high temperature range, and coke formation due to condensation may proceed between the reactants. If the reaction temperature is too low, the reaction does not proceed or the hydrogenation reaction proceeds and BTX conversion becomes difficult . Also, the effect of pressure is opposite to that of temperature. If the pressure is too high, hydrogenation predominates and paraffinic products may predominate. If the pressure is lower than the above range, coke formation by dehydrogenation Which is not preferable.
The hydrocracking reaction process is preferably operated by introducing hydrogen and a shape-selective catalyst.
The shape-selective catalyst is preferably a metal component selected from the group consisting of Group 6, Group 8, Group 9 and Group 10 of the periodic table.
The metal component is preferably selected from the group consisting of Ni 2 P, Co 2 P, Fe 2 P, MoP, WP, MoS 2 , Ni-MoS 2 , Ni-WS 2 and Co-MoS 2 .
The shape-selective catalyst preferably further comprises at least one shape-selective carrier selected from the group consisting of zeolite, ZSM-5, beta zeolite, Y-zeolite, USY-zeolite, mordenite and silica alumina.
The hydrocracking reaction process is operated under the conditions of a temperature of 200 to 1,000 ° C., a hydrogen partial pressure of 10 to 200 atm, a hydrogen content of 50 to 400 Nm 3 / kl, and a LHSV (liquid hourly space velocity) of 0.5 to 10.0 hr -1 . The above-mentioned reaction condition is an optimum condition for allowing the hydrogenation and the decomposition reaction to coexist, and is a condition suitable for hydrotreating the feed oil by partial hydrogenation. If the reaction conditions are out of the above range, hydrogenation is disadvantageous in the high temperature range, and coke formation due to condensation may proceed between the reactants. If the reaction temperature is too low, the reaction does not proceed or the hydrogenation reaction proceeds only to the conversion to BTX . Also, the effect of pressure is opposite to that of temperature. If the pressure is too high, hydrogenation predominates and paraffinic products may predominate. If the pressure is lower than the above range, coke formation by dehydrogenation Which is not preferable.
With regard to the second aspect of the present invention, the method of obtaining the monocyclic aromatic compound of the present invention is characterized in that LCO (light cycle oil) is added and operated in a hydrogen desulfurization and denitrification process in the presence of hydrogen and a catalyst, Removing the oil containing the compound and the nitrogen compound to obtain a partially hydrogenated oil fraction containing an aromatic compound and introducing and operating the partially hydrogenated oil fraction in the presence of hydrogen and a shape selective catalyst in a hydrocracking reaction process, And removing the unconverted oil containing the above aromatic compound to obtain a monocyclic aromatic compound.
It is preferable that the shape-selective catalyst is Ni 2 P in which the amount of Ni supported on the beta zeolite is 0.5 to 1.5 mmol / g, more preferably 0.7 mmol / g. When the loading amount of Ni is less than 0.5 mmol / g, the hydrogenation function of the catalyst is weak and the aromatic compound having two or more rings is increased by the dehydrogenation reaction. When the loading amount is more than 1.5 mmol / g, All of the aromatic compounds having a ring are saturated and conversion to paraffin or olefin is increased, which is not preferable.
The desulfurization reaction, the denitrification reaction, the thermal decomposition reaction, the dealkylation reaction, the transalkylation reaction, the alkylation reaction and the isomerization reaction of the aromatic components are performed in the reactors operated in the first and second aspects of the present invention described above Through such a reaction process, aromatic components such as benzene, toluene and xylene can be obtained.
Hereinafter, embodiments and embodiments of the present invention will be described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art.
1 is a schematic diagram showing a specific example of producing an aromatic product from PFO according to an embodiment of the present invention.
1, the PFO (S1) produced in the naphtha pyrolysis process contains sulfur compounds, aromatic compounds having one benzene ring, aromatic compounds having two benzene rings, and aromatic compounds having three or more benzene rings as compositional components Wherein the PFO (S1) is introduced into a distillation separation process (U1) and separated into a distillate (S2) which is an oil containing an aromatic compound having one or two sulfur compounds and benzene rings, and three benzene rings Or more of an aromatic compound having an aromatic group is separated into a residue (S3).
In the hydrodesulfurization / denitrification step (U2), the effluent (S2) reacts with hydrogen (S4) in the presence of a catalyst to separate the sulfur compound, which is a catalyst poisoning component, and reacts with hydrogen (S4) , An aromatic product (S5) containing toluene, xylene and an unmodified oil (S6). Here, the unmodified oil (S6) is mainly a sulfur compound and an oil containing an aromatic compound having two or more benzene rings.
2 is a schematic diagram illustrating a specific example of producing an aromatic product from an LCO according to an embodiment of the present invention.
2, the LCO (S1) produced in the fluidized bed catalytic cracking process contains sulfur compounds, nitrogen compounds, aromatic compounds having one benzene ring, aromatic compounds having two benzene rings, and aromatic compounds having three or more benzene rings The LCO (S1) enters the hydrogen desulfurization / denitrification process (U3) and reacts with hydrogen (S4) under catalytic conditions to remove sulfur compounds and nitrogen compounds (S3) ) Is introduced into the hydrocracking reaction process (U4). The reaction is carried out in the presence of a catalyst in the hydrocracking reaction step (U4) to convert and separate into an aromatic product (S5) containing benzene, toluene, xylene and unmodified oil (S6). Here, the unmodified oil (S6) is an oil containing mainly an aromatic compound having two or more benzene rings.
Hereinafter, the structure of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
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Example
>
Manufacturing example One : Ni 2 P / Beta Synthesis of Catalyst
A Ni 2 P / Beta catalyst, which is a catalyst supported on a zeolite Beta with a hydrogen-functional active catalyst, Ni 2 P, was prepared as follows. Commercial zeolite (Beta, Zeolyst) was used as a carrier for the production of shape selectivity catalyst. In order to support Ni 2 P catalyst, 8 wt% Ni component and 9 wt% P component were supported on the zeolite carrier by impregnation method. To this, 2.22 g (1.5 mmol Ni loading) of nickel nitrate, 2 g (3 mmol P loading) of ammonium phosphate dibasic and 1.3 ml of nitric acid were added to dissolve in 20 ml of distilled water. The thus prepared aqueous solution was impregnated into 5 g of the zeolite carrier while dropping by one drop. After the impregnation, it was dried in air at 120 DEG C for 8 hours. After drying, the mixture was calcined in air at 400 DEG C for 6 hours. After the completion of the calcination, the temperature was raised from room temperature to 600 캜 at a rate of 2 캜 / min while flowing hydrogen at a flow rate of 500 sccm.
Manufacturing example 2: 0.7 Ni 2 P / Beta Synthesis of Catalyst
In order to control the degree of hydrogenation of Ni 2 P catalyst, the amount of Ni 2 P supported was 0.7 mmol / g (Ni standard). The synthesis method is the same as in Production Example 1.
Manufacturing example 3: 1.5 Ni 2 P / Beta Synthesis of Catalyst
In order to control the degree of hydrogenation of Ni 2 P catalyst, the amount of Ni 2 P supported was 1.5 mmol / g (Ni standard). The synthesis method is the same as in Production Example 1.
Manufacturing example
4 :
NiMo
/
USY
Synthesis of Catalyst
The NiMo / USY catalyst, which is a catalyst supported on hydrous functional active catalyst, NiMo, in zeolite USY, was prepared as follows. 8 wt% of Mo component and 3 wt% of Ni component were supported on the zeolite USY support by impregnation method. For this purpose, an aqueous solution of (NH 4 ) 6 Mo 7 O 24 4H 2 O and an aqueous solution of Ni (NO 3 ) 2 6H 2 O (all Aldrich) were sequentially impregnated. After impregnation, drying at 120 ° C for 12 hours was carried out. Thereafter, the catalyst was calcined at 500 ° C. for 4 hours to synthesize NiMo / USY catalyst. In the reaction evaluation, 10% DMDS was pretreated for 2 hours at 350 ℃ for sulfidation treatment.
Manufacturing example
4 :
NiMo
/
Al
2
O
3
Synthesis of Catalyst
A NiMo / Al 2 O 3 catalyst, which is a catalyst loaded with NiMo on alumina, was prepared as follows. 8 wt% of Mo component and 3 wt% of Ni component were supported on the Al 2 O 3 support by impregnation method. For this purpose, an aqueous solution of (NH 4 ) 6 Mo 7 O 24 4H 2 O and an aqueous solution of Ni (NO 3 ) 2 6H 2 O (all Aldrich) were sequentially impregnated. After impregnation, drying at 120 ° C for 12 hours was carried out. And then calcined at 500 ° C. for 4 hours to synthesize a NiMo / Al 2 O 3 catalyst. In the reaction evaluation, 10% DMDS was pretreated for 2 hours at 350 ℃ for sulfidation treatment.
Example One
According to the method of the present invention, as shown in Table 1 below, PFO is used as a feedstock, it is subjected to simple distillation under atmospheric pressure to separate oil fractions having a boiling point of up to 300 ° C to obtain a two-ring aromatic, An aromatic product was prepared through the reaction (hydrogenated complex reaction).
The hydrodesulfurization / denitrification reaction was carried out in a fixed-bed reactor using the catalyst prepared in Preparation Example 1 and the catalyst supported on nickel-molybdenum in USY. The reaction conditions are shown in Table 2 below.
Table 3 shows the typical yield structures obtained from the operating conditions in Table 2 above.
In this embodiment, the performance of the process can be known by the yield of BTX, which is a product to be obtained in the present invention. Since the monoaromatic aromatic compound is a precursor which is converted into BTX, the higher the yield of the monoaromatic aromatic compound, the better the performance.
According to Table 3, when USY is used as a carrier, not only a single aromatic compound is decomposed due to a strong acid point, but also a coke is formed and a catalyst life is shortened. However, high BTX yields can be obtained if Beta is applied as a carrier.
As can be seen in Example 1 above, a high BTX yield can be achieved by applying a hydrodesulfurization / denitrification catalytic cracking process in the case of oils such as PFO with a low amount of sulfur and nitrogen compounds.
Example 2
Table 4 shows the properties of the LCO used in this example.
The LCO used in the present embodiment was obtained by using the cracked fraction of the fluidized bed catalytic cracking process, and the physical properties, composition and yield of the fluidized cracked cracked fraction produced according to the kind of the fluidized bed catalytic cracking raw material and the process operating conditions may be different have.
The raw material was introduced into the hydrotreating process. The hydrotreating process was carried out in a fixed bed reactor using a nickel-molybdenum combination catalyst. The reaction conditions of the hydrotreating process are shown in Table 5 below.
The typical yield structures obtained through the operating conditions of Table 5 are shown in Table 6. < tb >< TABLE >
As can be seen from the above table, before the hydrogenation reaction, a substantial amount of components containing two or more cyclic aromatics was present, but it was found that the amount of components containing the aromatic compound was drastically decreased after the hydrogenation reaction. The 1-ring aromatic component with naphthenic ring breaks the naphthenic ring in the subsequent fluidized-bed catalytic cracking and becomes a high value-added aromatic component or a direct source of high value-added aromatic component.
The feed produced in the hydrotreating process was introduced into the hydrocracking reaction process. The catalyst used here was a catalyst containing Ni 2 P supported on the beta zeolite, and the reaction conditions of the hydrocracking process are shown in Table 7.
Table 8 compares the feed components before and after the hydrocracking reaction.
In the present embodiment, the performance of the process can be known by the yield of BTX, which is a product to be obtained in the present invention. Since the monocyclic aromatic compound is a precursor which is converted into BTX, the higher the yield of the monocyclic aromatic compound, the better the performance.
According to Table 8, it can be seen that the 1.5Ni 2 P / Beta catalyst is predominantly hydrogenated and the catalytically cracked product is hydrogenated and converted to a light gas fraction. Which is unsuitable for obtaining BTX and mono-cyclic aromatic components to be obtained in the present invention. However, when the amount of Ni 2 P supported is reduced to 0.7, a high BTX yield can be obtained by proper hydrogenation reaction.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, This is possible.
U1: distillation separation process
U2: Hydrodesulfurization / denitrification and decomposition process
U3: Hydrogen desulfurization / denitrification process
U4: hydrocracking reaction process
Claims (27)
Characterized in that the method comprises the following steps:
(1) LCO (light cycle oil) is added and operated in a hydrogen desulfurization and denitrification process in the presence of hydrogen and a catalyst to remove oil containing sulfur compounds and nitrogen compounds, and partial hydrogenation oil fractions ;
(2) adding and operating the partially hydrogenated oil fraction in a hydrocracking reaction process in the presence of hydrogen and a shape selective catalyst to remove unconverted oil fractions containing an aromatic compound having two or more rings to obtain a single ring aromatic compound step.
Wherein said hydrodesulfurization, denitrification and partial hydrogenation processes and hydrocracking reaction processes are operated in a batch reactor, a continuous fixed bed reactor or a continuous fluidized bed reactor.
Wherein the hydrodesulfurization, denitrification and partial hydrogenation processes and the hydrocracking reaction process are hydrotreated combined reaction processes operated at the same time.
Wherein the oil introduced into the hydrotreating complex reaction step is PFO.
Wherein the hydrotreating complex reaction process is operated by introducing hydrogen and a shape selective catalyst.
Wherein the shape-selective catalyst is at least one member selected from the group consisting of Group 6, Group 8, and Group 9 elements of the periodic table, at least one member selected from the group consisting of zeolite, ZSM-5, beta zeolite, Y-zeolite, USY- zeolite, And a Group 10 metal compound.
Wherein the metal component is selected from the group consisting of Ni 2 P, Co 2 P, Fe 2 P, MoP, WP, MoS 2 , Ni-MoS 2 , Ni-WS 2 and Co-MoS 2 .
The hydrotreated complex reaction process is operated under conditions of a temperature of 200 to 1,000 ° C., a hydrogen partial pressure of 10 to 200 atm, a hydrogen content of 50 to 400 Nm 3 / kL, and a LHSV (liquid hourly space velocity) of 0.5 to 10.0 hr -1 ≪ / RTI >
The hydrogen desulfurization, denitrification and partial hydrogenation processes are carried out at a temperature of 200 to 500 ° C., a hydrogen partial pressure of 10 to 100 atm, a hydrogen content of 50 to 400 Nm 3 / kL, a liquid hourly space velocity (LHSV) of 0.5 to 5.0 hr -1 Lt; RTI ID = 0.0 > 1, < / RTI >
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| WO2012161281A1 (en) | 2011-05-24 | 2012-11-29 | Ｊｘ日鉱日石エネルギー株式会社 | Method for producing monocylic aromatic hydrocarbons |
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